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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Molecular Geometry and Electronic Structure of Copper Corroles

Copper corroles are known for their unique multiconfigurational electronic structures in the ground state, which arise from the transfer of electrons from the π orbitals of the corrole to the d-orbital of copper. While density functional theory (DFT) provides reasonably good molecular geometries, the determination of the ground spin state and the associated energetics is heavily influenced by functional choice, particularly the percentage of the Hartree–Fock exchange. Using extended multireference perturbation theory methods (XMS-CASPT2), the functional choice can be assessed. The molecular geometries and electronic structures of both the unsubstituted and the meso-triphenyl copper corroles were investigated. A minimal active space was employed for structural characterization, while larger active spaces are required to examine the electronic structure. The XMS-CASPT2 investigations conclusively identify the ground electronic state as a multiconfigurational singlet (S o ) with three dominant electronic configurations in its lowest energy and characteristic saddled structure. In contrast, the planar geometry corresponds to the triplet state (T o ), which is approximately 5 kcal/mol higher in energy compared to the S o state for both the bare and substituted copper corroles. Notably, the planarity of the T o geometry is reduced in the substituted corrole compared with that in the unsubstituted one. By analyzing the potential energy surface (PES) between the S o and T o geometries using XMS-CASPT2, the multiconfigurational electronic structure is shown to transition toward a single electron configuration as the saddling angle decreases (i.e., as one approaches the planar geometry). Despite the ability of the functionals to reproduce the minimum energy structures, only the TPSSh-D 3 PES is reasonably close to the XMS-CASPT2 surface. Significant deviations along the PES are observed with other functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Simulation of 24,000 Electron Dynamics: Real-Time Time-Dependent Density Functional Theory (TDDFT) with the Real-Space Multigrids (RMG)

Here, we present the theory, implementation, and benchmarking of a real-time time-dependent density functional theory (RT-TDDFT) module within the RMG code, designed to simulate the electronic response of molecular systems to external perturbations. Our method offers insights into nonequilibrium dynamics and excited states across a diverse range of systems, from small organic molecules to large metallic nanoparticles. Benchmarking results demonstrate excellent agreement with established TDDFT implementations and showcase the superior stability of our time integration algorithm, enabling long-term simulations with minimal energy drift. The scalability and efficiency of RMG on massively parallel architectures allow for simulations of complex systems, such as plasmonic nanoparticles with thousands of atoms. Future extensions, including nuclear and spin dynamics, will broaden the applicability of this RT-TDDFT implementation, providing a powerful toolset for studies of photoactive materials, nanoscale devices, and other systems where real-time electronic dynamics is essential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Computing the Relative Affinity of Chlorophylls a and b to Light-Harvesting Complex II

In plants and algae, the primary antenna protein bound to photosystem II is light-harvesting complex II (LHCII), a pigment–protein complex that binds eight chlorophyll (Chl) a molecules and six Chl b molecules. Chl a and Chl b differ only in that Chl a has a methyl group (–CH 3 ) on one of its pyrrole rings, while Chl b has a formyl group (–CHO) at that position. This blue-shifts the Chl b absorbance relative to Chl a . It is not known how the protein selectively binds the right Chl type at each site. Knowing the selection criteria would allow the design of light-harvesting complexes that bind different Chl types, modifying an organism to utilize the light of different wavelengths. The difference in the binding affinity of Chl a and Chl b in pea and spinach LHCII was calculated using multiconformation continuum electrostatics and free energy perturbation. Both methods have identified some Chl sites where the bound Chl type ( a or b ) has a significantly higher affinity, especially when the protein provides a hydrogen bond for the Chl b formyl group. However, the Chl a sites often have little calculated preference for one Chl type, so they are predicted to bind a mixture of Chl a and b . The electron density of the spinach LHCII was reanalyzed, which, however, confirmed that there is negligible Chl b in the Chl a -binding sites. Finally, it is suggested that the protein chooses the correct Chl type during folding, segregating the preferred Chl to the correct binding site.

chemical calculations↗
DOE OSTI2021

Using computational singular perturbation as a diagnostic tool in ODE and DAE systems: a case study in heterogeneous catalysis

We have extended the computational singular perturbation (CSP) method to differential algebraic equation (DAE) systems and demonstrated its application in a heterogeneous-catalysis problem. The extended method obtains the CSP basis vectors for DAEs from a reduced Jacobian matrix that takes the algebraic constraints into account. Here we use a canonical problem in heterogeneous catalysis, the transient continuous stirred tank reactor (T-CSTR), for illustration. The T-CSTR problem is modelled fundamentally as an ordinary differential equation (ODE) system, but it can be transformed to a DAE system if one approximates typically fast surface processes using algebraic constraints for the surface species. We demonstrate the application of CSP analysis for both ODE and DAE constructions of a T-CSTR problem, illustrating the dynamical response of the system in each case. We also highlight the utility of the analysis in commenting on the quality of any particular DAE approximation built using the quasi-steady state approximation (QSSA), relative to the ODE reference case.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

Probing coherent electronic superpositions of singly and doubly excited states of krypton with extreme-ultraviolet four-wave-mixing spectroscopy

Radiative nonlinear four-wave mixing can monitor the evolution of electronic wave packets, providing access to lifetimes and quantifying the light-induced couplings between excited states. In this article, we report the observation of quantum beats in an autoionizing electronic wave packet in krypton, probed using this technique. Analysis of the signal reveals that these beats originate from the contribution of previously unassigned, doubly excited states interacting with singly excited ones. We introduce a minimal theoretical model, based on multichannel quantum-defect theory, which quantitatively reproduces both the wave-packet dynamics and the static spectrum. This work combines a versatile, noncommensurate XUV-IR-based experimental scheme with a tractable model, establishing a powerful approach for the metrology and control of complex, correlated electronic states.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

One- and two-qubit gate infidelities due to motional errors in trapped ions and electrons

In this work, we derive analytic formulas that determine the effect of error mechanisms on one- and two-qubit gates in trapped ions and electrons. First, we analyze and derive expressions for the effect of driving field inhomogeneities on one-qubit gate fidelities. Second, we derive expressions for two-qubit gate errors, including static motional frequency shifts, trap anharmonicities, field inhomogeneities, heating, and motional dephasing. We show that, for small errors, each of our expressions for infidelity converges to its respective numerical simulation; this shows that our formulas are sufficient for determining error budgets for high-fidelity gates, obviating numerical simulations in future projects. All of the derivations are general to any internal qubit state, and any mixed state of the ion crystal's motion that is diagonal in the Fock state basis. Our treatment of static motional frequency shifts, trap anharmonicities, heating, and motional dephasing apply to both laser-based and laser-free gates, while our treatment of field inhomogeneities applies to laser-free systems.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Two-electron interference in two-photon attosecond double ionization of neon

The pump-probe experiments enabled by x-ray free-electron lasers (XFEL) will allow us to directly observe correlated electronic motion with attosecond time resolution by detecting photoelectron pairs in coincidence. In helium, the transition between the nonsequential and sequential regime in two-photon double ionization (TPDI) is well explained by a virtual-sequential model. Much less is known, however, about the TPDI process in more complex atoms. Recently, we extended the virtual-sequential model to arbitrary light pulses [Chattopadhyay Phys. Rev. A 108, 013114 (2023)]. This extension employs multichannel scattering states for the single ionization of both the neutral and the ionized target, which we initially applied to helium. In the present study, we show that our extended virtual-sequential model reproduces the qualitative features of the angularly integrated observables with available experimental results for neon, a considerably more complex target. We observe an intriguing feature of inverted two-particle interference in the joint-energy distribution of Ne compared to He. Finally, this phenomenon, attributable to the presence of a final doubly ionized state with triplet symmetry coupled to the two photoelectrons, should be observable with current experimental technologies.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Quantum interference between the optical Stark effect and resonant harmonic generation in WS 2

An applied field can modulate optical signals by resonance shifting via the Stark effect. The optical Stark effect uses ultrafast light in the transparency region of a material to shift resonances with speeds limited by the pulse duration or system coherence. In this Rapid Communication, we investigate the optical Stark effect in resonant optical harmonic generation using the A exciton transition of WS 2 . Multidimensional pump-harmonic-probe measurements, in which the probe is second- or third-harmonic emission, reveal not only large Stark shifts that are commensurate with the large optical susceptibilities common to WS 2 excitons, but also behaviors more complex than simple optical Stark effect treatments predict. We show how another manifestation of the Stark effect, brought forth by coherent photon exchange between the pump and harmonic generation fundamental fields, can strongly enhance or suppress harmonic generation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Entangled two-plasmon generation in carbon nanotubes and graphene-coated wires

Here, we investigate the two-plasmon spontaneous decay of a quantum emitter near single-walled carbon nanotubes (SWCNTs) and graphene-coated wires (GCWs). We demonstrate efficient, enhanced generation of two-plasmon entangled states in SWCNTs due to the strong coupling between tunable guided plasmons and the quantum emitter. We predict two-plasmon emission rates more than twelve orders of magnitude higher than in free space, with average lifetimes of a few dozen nanoseconds. Given their low dimensionality, these systems could be more efficient for generating and detecting entangled plasmons in comparison to extended graphene. Indeed, we achieve a tunable spectrum of emission in GCWs, where sharp resonances occur precisely at the plasmons' minimum excitation frequencies. We show that by changing the material properties of the GCW's dielectric core, one could tailor the dominant modes and frequencies of the emitted entangled plasmons while keeping the decay rate ten orders of magnitude higher than in free space. By unveiling the unique properties of two-plasmon spontaneous emission processes in the presence of low-dimensional carbon-based nanomaterials, our findings set the basis for a novel material platform with applications to on-chip quantum information technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Constraints on dark matter from dynamical heating of stars in ultrafaint dwarfs. II. Substructure and the primordial power spectrum

There is a large and growing interest in observations of small-scale structure in dark matter. We propose a new way to probe dark matter structures in the ∼ 10 – 10 8 M ⊙ range. This allows us to constrain the primordial power spectrum over shorter distances scales than possible with direct observations from the CMB. For k in the range ∼ 10 – 1000 Mpc − 1 our constraints on the power spectrum are orders of magnitude stronger than previous bounds. We also set some of the strongest constraints on dark matter isocurvature perturbations. Our method relies on the heating effect such dark matter substructures would have on the distribution of stars in an ultrafaint dwarf galaxy. Many models of inflation produce enhanced power at these short distance scales and can thus be constrained by our observation. Further, many dark matter models such as axion dark matter, self-interacting dark matter and dissipative dark matter, produce dense structures which could be constrained this way. Published by the American Physical Society 2024

Graham, Peter W. (ORCID:0000000216001601)↗
DOE OSTI2021

Quasisymmetric Optimization of Nonaxisymmetry in Tokamaks

Predictive 3D optimization reveals a novel approach to modify a nonaxisymmetric magnetic perturbation to be entirely harmless for tokamaks, by essentially restoring quasisymmetry in perturbed particle orbits as much as possible. Such a quasisymmetric magnetic perturbation (QSMP) has been designed and successfully tested in the KSTAR and DIII-D tokamaks, demonstrating no performance degradation despite the large overall amplitudes of nonaxisymmetric fields and strong response otherwise expected in the tested plasmas. The results indicate that a quasisymmetric optimization is a robust path of error field correction across the resonant and nonresonant field spectrum in a tokamak, leveraging the prevailing concept of quasisymmetry for general 3D plasma confinement systems such as stellarators. Finally, the optimization becomes, in fact, a simple eigenvalue problem to the so-called torque response matrices if a perturbed equilibrium is calculated consistent with nonaxisymmetric neoclassical transport.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Robust qubit interactions mediated by photonic topological edge states

Here, we investigate the coupling of two spatially separated qubits via topologically protected edge states in a two-dimensional Hofstadter lattice. In this hybrid platform, the qubits are coupled to distinct edge sites of the lattice, enabling long-range interactions mediated by topological edge modes. We solve the full system Hamiltonian and analyze the resulting eigenstate structure to uncover the conditions under which coherent qubit interactions emerge. Our analysis reveals that the effective coupling is highly sensitive to the qubit placement, energy detuning, and the topological character of the edge spectrum. We obtain an analytical solution that goes beyond the perturbative regime, capturing the full interplay between the qubits and edge modes. These results provide a foundation for exploring information transport and many-body effects in engineered quantum systems where interactions are mediated by topological edge modes.

Chern insulators↗
DOE OSTI2025

Neural refinement of sample weights

Monte Carlo simulations are an essential tool in particle physics data analysis. Events are typically generated alongside weights that redistribute the cross section of the simulated process across the phase space. These weights can be negative, and several post hoc methods have been developed to eliminate or mitigate the negative values. All of these methods share the common strategy of approximating the average weight as a function of phase space. We introduce an alternative approach, which, instead of reweighting to the average, refines the initial weights with a scaling transformation, utilizing a phase space-dependent factor. Since this new refinement method does not need to model the full weight distribution, it can be more accurate. High-dimensional and unbinned phase space is processed using neural networks for the refinement method. In addition to the refinement method, we introduce a new resampling protocol, which can be used in conjunction with any weight transformation to not only preserve the average weight but also the statistical uncertainties of the initial distribution. Using both realistic and synthetic examples, we show that the new neural refinement method is able to match or exceed the accuracy of similar weight transformations and that the new resampling protocol is simpler in implementation than previous methods while exhibiting equivalent statistical properties.

Artificial neural networks↗
DOE OSTI2021

Outcomes and Insights From Simplified Analytic Trajectory Optimization for a Tethered Underwater Kite

This letter formulates and solves a periodic trajectory optimization problem for a tethered underwater kite. The goal is to maximize the average mechanical power harvested by the kite. The type of kite considered in this letter extracts electricity from ocean currents by moving cross-current as its reel away from its base station, and consumes electricity to reel back. The problem of optimizing this kite’s trajectory is challenging due to the high dimensionality and nonlinearity of its dynamics. To tackle this challenge, the literature often separates the problem into two subproblems focusing on optimizing the cross-current and the reel-in/reel-out components of the trajectory, respectively, which may be sub-optimal. In contrast, this letter solves for the combined cross-current and reel-in/reel-out trajectory by linearizing the dynamics of the kite around a zero-power reference equilibrium trajectory in spherical coordinates. This allows the trajectory optimization problem to be solved analytically for simple sinusoidal input perturbations from equilibrium. Here we use linear quadratic regulation to enable the nonlinear kite model to track the optimized trajectory. The result is a computationally efficient approach that achieves an attractive Loyd factor of 19.9%, while providing important insights into the nature of the optimal trajectory.

42 ENGINEERING↗